US3704154A

US3704154A - Process for producing photographic materials

Info

Publication number: US3704154A
Application number: US116625A
Authority: US
Inventors: Sumitaka Tatsuta; Wataru Ueno
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1970-02-20
Filing date: 1971-02-18
Publication date: 1972-11-28
Anticipated expiration: 1989-11-28
Also published as: CA927687A; NL7101888A; SE357630B; DE2107883A1; GB1299166A; JPS5224406B1; FR2078831A5

Abstract

A PROCESS FOR PRODUCING PHOTOGRAPHIC MATERIALS COMPRISING CONTACTING A BI-AXIALLY STRETCHED POLYSTYRENE SUPPORT WITH A LIQUID CONTAINING AT LEAST A SOLVENT OR SWELLING AGENT FOR SAID POLYSTYRENE AND GELATIN DISPERSED THEREIN, CONTACTING THE SUPPORT WITH A NON-SOLVENT FOR SAID POLYSTYRENE TO PREPARE A WHITE OPAQUE POLYSTYRENE SUPPORT HAVING A HYDROPHILIC SURFACE, AND APPLYING AN EMULSION OR SUSPENSION CONTAINING GELATIN TO SAID SUPPORT, IS DISCLOSED.

Description

United States Patent Oifice Patented Nov. 28, 1972 PROCESS FOR PRODUCING PHOTOGRAPHIC MATERIALS Sumitaka Tatsuta and Wataru Ueno, Kanagawa, Japan,

assignors to Fuji Photo Film Co., Ltd., Kanagawa,

Japan No Drawing. Filed Feb. 18, 1971, Ser. No. 116,625

Claims priority, application Japan, Feb. 20, 1970, 45/ 14,938 Int. Cl. 341m /14; G03c 1/76 US. Cl. 117-34 4 Claims ABSTRACT OF THE DISCLOSURE A process for producing photographic materials comprising contacting a bi-axially stretched polystyrene support with a liquid containing at least a solvent or swelling agent for said polystyrene and gelatin dispersed therein, contacting the support with a non-solvent for said polystyrene to prepare a white opaque polystyrene support having a hydrophilic surface, and applying an emulsion or suspension containing gelatin to said support, is disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a process for producing photographic materials having a light-sensitive layer containing gelatin or an image receiving layer which is used for a silver salt diffusion transfer process on a white opaque polystyrene support (the so-called synthetic paper).

(2) Description of the prior art Hitherto, as the support of the photographic paper, baryta paper which is prepared by coating the paper produced from pulp with barium sulfate has been used. However, this support has disadvantages, for example, expansion and contraction caused by temperature variation and especially contraction which results after developing treatment, drying after development requires a long period of time, and the support has poor resistance in water.

Such disadvantages are resolved by using films of hydrophobic high molecular substances, for example, a biaxially stretched polystyrene film as the support of the photographic printing paper.

In this case, however, the support should be whitened opaquely. This procedure is carried out using a method which comprises dipping a polystyrene film in a solvent or a swelling agent for polystyrene, such as tetrahydro furan, ethyl acetate and acetic acid, and dipping the film then in a non-solvent for polystyrene, such as methanol and ethanol, to form a coarse surface.

This support is markedly preferred as the support of a photographic paper because of its excellent water resistance, drying rate, dimensional stability, rigidity, whiteness and opacity.

However, although the polystyrene has the abovedescribed excellent characteristics as the support of photographic printing paper, it is very difiicult to cause a film formed from photographic emulsions containing hydrophilic gelatin to adhere firmly to the surface of the sup port, because it is hydrophobic and chemically inactive. As a means of changing the hydrophobic surface into a hydrophilic one, treatments such as corona discharge, electron ray application and ozone oxidation, and the like, are disclosed already in Japanese patent application No. Sho 44-98485, Sho 45-20695 and Sho 45-4163.

SUMMARY OF THE INVENTION The process by this invention, which does not contain the above-described tWo steps, that is, comprising whitening opaquely a transparent polystyrene support at first and then performing a hydrophilic treatment of the resulting surface, is characterized in that photographic materials are prepared by Whitening opaquely the transparent polystyrene support and preparing a hydrophilic surface at the same time, and applying an emulsion or a suspension containing gelatin to the resulting surface, by which adhesion between the support and the coating film is improved.

Namely, the present invention is a process for preparing photographic materials which comprises contacting a biaxially stretched polystyrene support with a liquid which comprises at least a solvent or swelling agent for polystyrene and gelatin dispersed therein, then contacting the support with a non-solvent for polystyrene to prepare a white opaque polystyrene support having a hydrophilic surface, and applying an emulsion or a suspension containing gelatin to said polystyrene support.

DETAILED DESCRIPTION OF THE INVENTION In this invention, the emulsion or suspension containing gelatin applied to the polystyrene means an aqueous emulsion or aqueous suspension of gelatin which can be prepared by adding or not adding a silver halide, such as silver chloride, silver bromide, silver chlorobromide and silver iodobromide, a light-sensitive diazo compound, substance of center of development of the image receiving material used in the silver salt diffusion transfer process, and other desired substances. After application of the aqueous gelatin solution, the silver halide emulsion may be applied. In this case, the coating film made from the aqueous gelatin solution is a subbing layer for application of emulsions.

As described above, a fine porous layer is formed on the bi-axially stretched polystyrene support by contacting said polystyrene support with a solvent or swelling agent thereof and then contacting the support with a nonsolvent for polystyrene which can be compatible with said solvent or swelling agent, by which said support becomes very white and opaque.

When subjected to permeation of the above-described solvent or swelling agent into the polystyrene support, if gelatin particles are dispersed in the solvent or swelling agent, the gelatin particles precipitate simultaneously with the formation of a fine porous layer, by which the polystyrene support becomes white and opaque and the surface thereof becomes hydrophilic at the same time. Thus, the adhesive strength between the resulting white opaque and hydrophilic polystyrene support and a photographic emulsion layer containing gelatin or an image receiving coating layer in the silver salt difiusion transfer process (hereinafter, such a layer will be described as an image receiving layer) is large both in the dry state and in the wet state on development treatment.

The solvent and the swelling agent which can be used in the above-described treatment include, for example, methyl acetate, ethyl acetate, acetone, methylethylketone, methylene chloride, ethylene chloride, tetrahydrofuran, cyclohexane, benzene, dioxane, benzyl alcohol, trichlene and mixtures thereof. The non-solvent includes methanol and ethanol and the like. In this invention, water, nonsolvents and dispersing agents may be, added suitably on dispersing the aqueous gelatin solution in said solvent or swelling agent. Further, although the amount of gelatin dispersed depends upon type of solvent, from 0.1 to 2.0% by weight or so is preferable.

The adhesive strength between the thus resulting support and the photographic emulsion layer containing gelatin or the image receiving layer does not exhibit any deterioration after the passage of long periods of time.

Methods of testing the adhesive strength between the photographic emulsion layer or image receiving layer and the film support in examples of this invention were as follows.

(1) Method of testing the adhesive strength in the dry state A cellulose triacetate film of 0.14 mm. thickness is adhered to a surface of the emulsion layer or image receiving layer of the film support using an epoxy adhesive. After letting stand at 23 C., 65% RH for a day, the resulting film is cut in a strip 1 cm. in width and 15 cm. in length. The strip is then stripped off at a drawing rate of 7.38 cm./min. The stripping strength is determined by strain gauge. In the examples of this invention, good adhesion means the stripping strength is larger than 8 g./mm., which in practice is sufiicient as the adhesive strength between the emulsion layer or image receiving layer and the support in photographic materials.

(2) Method of testing the adhesive property in the wet state In steps of developing, fixing and rinsing, the same test of stripping as in the above-described method is practiced, using a cyanoacrylate type adhesive. Good adhesion means having a stripping strength greater than 2 g./mm.

EXAMPLE 1 After dipping a bi-axially stretched polystyrene support 0.1 mm. in thickness in a solution having the following composition at 20 C. for 3 seconds, the support was dipped in methanol for another 30 seconds to prepare a hydrophilic white opaque polystyrene.

Gelatin aqueous solution) cc 8 Salicylic acid (dispersing agent) g 0.3 Ethylene chloride cc 50 Methanol cc 50 Formalin (20% aqueous solution) cc 0.3

To the white opaque polystyrene support having hydrophilic surfaces above-described, a gelatin-silver halide photographic emulsion having the following composition per 1 111. of the film was applied:

Silver chlorobromide (chlorine:bromine=30 mols:

70 mols) g v 3.5 Gelatin 13.0 Formalin (hardening agent) 0.1 Saponin 0.03

atin was not dispersed and with the above-described emulsion being then applied, adhesion in the dry state and the wet state was quite inferior, that is, the stripping strength was less than 2 g./ mm. in the dry state and nearly 0 g./mm. in the wet state.

EXAMPLE 2 After dipping a bi-axially stretched polystyrene support 0.1 mm. in thickness in a solution having the following composition at 20 C. for 3 seconds, the support was further dipped in methanol for 30 seconds to prepare a white opaque hydrophilic polystyrene support.

Gelatin (10% aqueous solution) cc 4 Salicylic acid (dispersing agent) g 0.3 Benzene cc 50 Acetone cc 50 Formalin (20% aqueous solution) cc 0.3

To the white opaque polystyrene having hydrophilic surfaces above-described, a coating solution of the image receiving layer used in a silver salt diffusion transfer process having the following composition per 1 m. of the film was applied.

Gelatin 3 Ag S colloid 0.001 Phenylmercaptotetrazole 0.01 Saponin 0.02

EXAMPLE 3 After dipping a bi-axially stretched polystyrene support 0.2 mm. in thickness in a solution having the following composition at 20 C. for 3 seconds, the support was further dipped in methanol for 30 seconds to prepare a white opaque polystyrene support having hydrophilic surfaces.

Gelatin (10% aqueous solution) cc 8 Salicylic acid g 0.3 Methylene chloride cc 50 Methanol cc.. 50 Formalin (20% aqueous solution) cc 0.3

To the opaquely whitened polystyrene support having hydrophilic surfaces, a gelatin-silver halide color photographic emulsion having the following composition per 1 m. of the film was applied.

Silver chlorobromide (chlorine:bromine=30 mols:

70 mols) g 3.0 Gelatin g 3.5 Emulsified dispersion containing benzoyl-aceto-Z- chloro-S-dodecyloxycarbonyl anilide (yellow coupler) g 14.0 Triethylene phosphamide (3% acetone solution) ml 3.0 Polyvinylpyrrolidone g 0.7

When the test of stripping the emulsion layer from the support was practiced on the above-described color photographic emulsion coating film, it exhibited satisfactory adhesive strength in both the dry state and the wet state for the color photographic material.

On the contrary, when the transparent polystyrene was treated with the above-described solution in which gelatin was not dispersed followed by subsequently applying the above-described color emulsion, adhesion of the film was quite inferior.

What is claimed is:

1. A process for producing photographic materials which comprise a photographic layer on a support having increased adherence between the photographic layer and the support, said process comprising contacting a biaxially stretched polystyrene support with a liquid containing at least a solvent or swelling agent for said polystyrene and from 0.1 to 2.0% by weight of gelatin dispersed therein, contacting the support with a non-solvent for said polystyrene to simultaneously render said polystyrene support white opaque and having a hydrophilic surface and applying a photographic emulsion or suspension containing gelatin to the white opaque hydrophilic surface of said support.

2. The process of claim 1, wherein said solvent or swelling agent is selected from the group consisting of methyl acetate, ethyl acetate, acetone, methylethylketone, methylene chloride, ethylene chloride, tetrahydrofuran, cyclohexane, benzene, dioxane, benzyl alcohol, trichlene and mixtures thereof, and wherein said non-solvent is selected from the group consisting of methanol and ethanol.

3. The process of claim 1, wherein said emulsion or suspension containing gelatin contains a member selected from the group consisting of a silver halide, a light-sensitive diazo compound, and a material providing centers of development of an image receiving material in a silver salt diffusion transfer process.

4. The process of claim 1, wherein said emulsion or suspension containing gelatin forms a subbing layer.

References Cited UNITED STATES PATENTS 2,957,791 10/1960 Bechtold 96-87 3,515,567 6/1970 Tani et al 117--47 A 3,547,642 12/1970 Nishio et al. 96-84 3,357,874 12/1967 Kennedy et al. 117-47 A 3,124,476 3/1964 Park et al. 117-47 A 3,132,983 5/ 1964 Osborne et al 117-47 A 2,790,727 4/1957 I-Iilborn 117-63 2,848,752 8/ 1958 Bechtold 11736.7 3,135,622 6/19'54 Ranalli 11763 3,298,895 11/ 1967 Plambecki 117-36.7 3,146,883 9/1964 Harlan et al. 117--47 A WILLIAM D. MARTIN, Primary Examiner W. R. TRENOR, Assistant Examiner US. Cl. X.R.

117--l1, 47 A, 36.7, 63, 117, 138.8 UA; 96--84, 87